Interpenetrating digold(I) diacetylide macrocycles

Article abstract of DOI:10.1039/b201832b

The cyclic dialkynyldigold(I) complexes [1,2-C₂H₄(O-3-C₆H₄OCH ₂CCAu)₂(μ-LL)] were prepared by reaction under basic conditions of the dialkyne 1,2-C₂H₄(O-3-C₆

Full text of DOI:10.1039/b201832b

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Interpenetrating digold(I) diacetylide macrocycles
William J. Hunks,a Jennifer Lapierre,a Hilary A. Jenkinsb and Richard J. Puddephatt*a
a Department of Chemistry, University of Western Ontario, Canada N6A 5B7.
E-mail: pudd@uwo.ca
b Department of Chemistry, St. Mary’s University, Halifax, Canada B3H 3C
Received 19th February 2002, Accepted 9th May 2002
First published as an Advance Article on the web 7th June 2002
The cyclic dialkynyldigold() complexes [1,2-C2H4(O-3-C6H4OCH2CCAu)2(µ-LL)] were prepared by reaction
under basic conditions of the dialkyne 1,2-C2H4(O-3-C6H4OCH2CCH)2 with [AuCl(SMe2)] and the corresponding
᎐
diphosphine ligands LL = Ph P(CH ) PPh (n = 1–6), trans-Ph PCH᎐CHPPh and Ph PC᎐CPPh . The new
᎐
᎐
2
2
n
2
2
2
2
2
organometallic macrocycles have ring sizes ranging from 23 to 28 atoms, and the complexes with LL = Ph2P(CH2)4-
PPh and trans-Ph PCH᎐CHPPh have been structurally characterized. In both cases, the digold() macrocycles
᎐
2
2
2
assemble into dimers in the solid state through Au ؒ ؒ ؒ Au aurophilic bonding, with a phenyl group of each
macrocycle occupying the cavity of the other. However, this extensive interpenetration occurs without the
catenation observed in some similar complexes. The complexes give room temperature emissions above 400 nm in
solution and the solid state, and a red shift of approximately 50 nm between emission maxima in the solution and
the solid state spectra is suggested to be an indication of the strong interpenetration in the solid state.
Introduction
The construction of macrocyclic complexes that incorporate
large cavities is a rapidly developing area of research, since
these compounds have potential for useful host–guest inter-
actions and can form mechanically bonded supermolecules,
such as rotaxanes and catenanes.1 In particular, macrocycles
containing metal–acetylide linkages have shown promise in the
construction of electronic or optical devices,2 or as luminescent
chemical sensors.3 Since polynuclear alkynylgold() complexes
exhibit luminescent behavior,4 they have been used as pendant
groups to an attached macrocycle or within the macrocycle in
sensors for the selective recognition of guest molecules.5 The
chromophore units respond with changing emission intensity
and/or wavelength upon coordination of guest analytes. In addi-
tion, the linear two-coordinate geometry of gold() is ideal
for forming molecules containing cavities,6 and the common
presence of secondary Au ؒ ؒ ؒ Au (aurophilic) bonds, having
strengths of 5–11 kcal molϪ1 and distances from 2.75–3.60 Å,
can promote supramolecular association of several kinds.
Some known digold() macrocyclic complexes containing
diacetylide and diphosphine bridging ligands are illustrated in
Chart 1.7 Using the digold() diacetylides derived from o-, m-,
and p-bis(propargyloxy)benzene and the diphosphines Ph2P-
(CH2)nPPh2 (n = 1–6), macrocyclic complexes A containing
15–22 membered rings were prepared,7a but the relatively
small cavity size did not allow strong intermolecular associ-
ation. With rigidly linear or angular diacetylides, tetragold()
complexes B (Ar = 1,4-C6H4 or 4,4Ј-C6H4C6H4), contain-
ing larger 26- or 34-membered rings, or C, containing larger
24-membered rings were obtained, but the stretched rings were
long and too narrow to allow intertwining.7b,c However, the ring
complexes such as D, with a hinge group X = O, S, CH2, CMe2,
or C6H10 (cyclohexylidene) and diphosphine ligands, Ph2P-
(CH2)nPPh2, chosen to give 23–27 membered rings by varying n,
gave more complex behavior. If X = O or S, the compounds
gave simple rings in all cases studied but, when X = CH2
or CMe2 and n = 3–6, the compounds self-assembled to give
[2]catenanes such as E (n = 4) and, when X = C6H10 and n = 4,
even a doubly braided [2]catenane was obtained.7d,e This raised
the question of what would happen if a multiple atom bridge X
was used, thus giving both larger ring size and, if X is a flexible
chain, greater ring distortions. Since it is known that secondary
Chart 1 Macrocyclic dialkynyl(diphosphine)gold() complexes.
C–H ؒ ؒ ؒ O interactions can aid in the assembly of supra-
molecular entities having the ability to selectively bind guest
molecules,8 it was decided to explore the effect of incorporating
ether spacer units X in rings of type D. This paper reports the
first example of such a series, incorporating an ethylene glycol
spacer unit, X = OCH2CH2O. Macrocyclic complexes contain-
ing bridging diacetylide and diphosphine ligands with ring sizes
of 23–28 atoms have been prepared, and two of these are shown
to pack as face to face centrosymmetric pairs, with marked
interpenetration and which are joined through Au ؒ ؒ ؒ Au
bonding. Previously, linear chains of rings linked side by side
DOI: 10.1039/b201832b
J. Chem. Soc., Dalton Trans., 2002, 2885–2889
This journal is © The Royal Society of Chemistry 2002
2885

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Table 1 Selected bond parameters (Å,Њ) for complex 3g
through Au ؒ ؒ ؒ Au bonding, and cationic gold rings linked
through bridging dicyanoaurate() anions, were reported.7 It is
also important to note that gold() is often a labile metal center
and that the facile exchange of gold-phosphine groups often
allows the synthesis of interconnected complexes.9
Au(1)–C(71)
Au(1)–P(1)
C(7)–C(8)
2.020(6)
2.273(1)
1.170(8)
3.0161(3)
Au(2)–C(8)
Au(2)–P(2)
C(71)–C(70)
2.026(6)
2.274(1)
1.166(9)
Au(1)–Au(2)
C(71)–Au(1)–P(1)
C(71)–Au(1)–Au(2)
P(1)–Au(1)–Au(2)
C(70)–C(71)–Au(1)
C(10)–P(1)–Au(1)
175.9(2)
85.7(2)
96.93(4)
175.6(6)
115.7(2)
C(8)–Au(2)–P(2)
174.0(2)
Results and discussion
C(8)–Au(2)–Au(1)
P(2)–Au(2)–Au(1)
C(7)–C(8)–Au(2)
C(9)–P(2)–Au(2)
91.8(2)
93.87(4)
169.8(6)
111.4(2)
Synthesis and spectra of the complexes
᎐
The ligand 1,2-C H (O-3-C H OCH C᎐CH) , 1, was prepared
᎐
2
4
6
4
2
2
from 3,3-(ethylenedioxy)diphenol and 3-bromopropyne in the
presence of base, according to Scheme 1. The complex was
The structures of complexes 3d and 3g
The structures of complexes 3d and 3g (Scheme 1) were
determined crystallographically. The structure of 3g, LL =
trans-Ph CH᎐CHPPh , is shown in Fig. 1 and selected distances
᎐
2
2
Scheme
1
Synthesis of the macrocyclic complexes. Reagents:
(i) BrCH2CCH, K2CO3; (ii) [AuCl(SMe2)], NaOAc; (iii) LL.
isolated as a pale yellow solid and characterized using NMR,
IR, and MS. In the 1H NMR spectrum, the alkyne proton
appeared as a triplet at δ = 2.39, due to coupling to the
OCH2CC protons at 4.67 ppm, with 4J(HH) = 2 Hz. In the IR,
an intense band at 2116 cmϪ1 was assigned to ν(C᎐C) while two
᎐
᎐
peaks at 3289 and 3267 cmϪ1 were assigned to ν(C᎐C–H).
᎐
᎐
᎐
Fig. 1 The structure of complex 3g, [1,2-C2H4(O-3-C6H4OCH2C᎐
The dialkyne, 1, was readily converted to the oligomeric
᎐
CAu)2(µ-trans-Ph2PCH᎐CHPPh2)], showing the association of two
᎐
᎐
alkynylgold() complex, [1,2-C H (O-3-C H OCH C᎐CAu) ] ,
᎐
2
4
6
4
2
2 n
rings through Au ؒ ؒ ؒ Au bonding: (a) the macrocyclic ring structure
and Au ؒ ؒ ؒ Au bonds (phenyl groups and hydrogen atoms are omitted
for clarity); and (b) a space-filling model with all atoms included,
illustrating the penetration of a phenyl group through each cavity.
Symmetry operations for equivalent atoms: Ϫx ϩ 2, Ϫy ϩ 1, Ϫz ϩ 1.
2, by reaction with [AuCl(SMe2)] in the presence of base, as
shown in Scheme 1. Complex 2 was isolated as an insoluble,
᎐
deep yellow solid. In the IR spectrum, the C᎐C stretching
᎐
frequency (2000 cmϪ1) was reduced by 116 cmϪ1 compared to
1, presumably because the gold atoms form a coordination
polymer through both σ and π-bonding to the alkynyl groups.10
The insoluble polymeric alkynylgold() complex was converted
and angles are in Table 1. Fig. 1a shows that the complex exists
as a 24-membered ring containing a diacetylide and a diphos-
phine ligand bridging between two gold() centers, and that
these rings are closely associated into pairs through inter-ring
Au ؒ ؒ ؒ Au bonding. There is a center of symmetry located in
the center of the resulting tetragold() aggregate, but the
two rings are not catenated and so would be expected to exist
separately in solution. The two rings in 3g cross each other
with corresponding dihedral angles C–Au ؒ ؒ ؒ Au–C = 57Њ and
P–Au ؒ ؒ ؒ Au–P = 52Њ. The distances Au–C = 2.020(6) Å
and Au–P = 2.273(1) Å are typical for alkynyl(phosphine)-
gold() complexes.4–7 The independent angles P–Au–C =
175.9(2) and 174.0(2)Њ are somewhat distorted from linearity,
to the soluble macrocyclic complexes [1,2-C2H4(O-3-C6H4-
᎐
OCH C᎐CAu) (µ-LL)], 3, by reaction with the corresponding
᎐
2
2
diphosphine ligand, LL, as illustrated in Scheme 1. The com-
plexes 3 were isolated as white powders, that were soluble in
dichloromethane or nitrobenzene, and characterized by their
IR and NMR spectra. For example, in the IR spectrum, com-
Ϫ1
᎐
plex 3b gave a single weak band due to ν(C᎐C) at 2130 cm
.
᎐
In the 31P NMR spectrum, a single resonance was observed
1
at δ = 40.04, while in the H NMR spectrum the OCH2CC
and OCH2CH2O resonances appeared as singlets at δ = 4.79 and
4.32, respectively.
2886
J. Chem. Soc., Dalton Trans., 2002, 2885–2889

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Table 2 Selected bond parameters (Å,Њ) for complex 3d
Au(1)–C(1)
Au(1)–P(1)
C(1)–C(2)
2.05(2)
2.260(5)
1.16(3)
3.074(1)
Au(2)–C(20)
Au(2)–P(2)
C(19)–C(20)
2.06(3)
2.281(6)
1.01(3)
Au(1)–Au(2)
C(1)–Au(1)–P(1)
C(1)–Au(1)–Au(2)
P(1)–Au(1)–Au(2)
C(2)–C(1)–Au(1)
C(61)–P(1)–Au(1)
172.9(5)
84.3(5)
102.7(1)
174(2)
C(20)–Au(2)–P(2)
C(20)–Au(2)–Au(1)
P(2)–Au(2)–Au(1)
C(19)–C(20)–Au(2)
C(65)–P(2)–Au(2)
175.9(5)
87.5(5)
96.5(1)
164(2)
111.1(6)
115.0(7)
and the distortion is in the sense that allows a closer Au ؒ ؒ ؒ Au
contact. The intermolecular Au ؒ ؒ ؒ Au distance of 3.0161(3) Å
indicates a strong aurophilic attraction, optimised by the
crossed alignment of the associated C–Au–P groups,11 while the
intramolecular, transannular Au ؒ ؒ ؒ Au distance of 6.303 Å is
much too long for bonding.
Each ring in 3g contains a large cavity, with longest trans-
annular dimensions of 11.12
Å
between the opposite
᎐
OCH C᎐C atoms, and 9.41 Å between the OCH CH and
᎐
2
2
2
Ph PCH᎐ atoms. The angle between the planes of the two aryl
᎐
2
groups of each C6H4OCH2CH2OC6H4 unit is 92Њ, with one ring
lying roughly in the plane and the other roughly perpendicular
to the macrocycle. The two rings are twisted but they are
stacked roughly parallel. A remarkable feature of the structure
is that a phenyl-phosphine group of one ring extends fully
through the cavity of the other ring, as depicted in Fig. 1b.
There are several secondary inter-ring aryl ؒ ؒ ؒ aryl contacts
which, together with the Au ؒ ؒ ؒ Au bonding, provides strong
binding of the two rings (Fig. 1b). Clearly the net inter-ring
attractions are stronger in this observed structural form com-
pared to the catenated structure analogous to E (Chart 1).
The structure of 3d, LL = Ph2P(CH2)4PPh2, is shown in Fig. 2
with selected bond distances and angles in Table 2. The data
were of poor quality, with disordered dichloromethane
solvent molecules in the lattice, but the important structural
features of the complex are clearly determined. The structure
is similar to that of 3g (Fig. 1). There is a 26-membered
ring containing a diacetylide a diphosphine and two gold()
centers, and two such rings are tightly associated but not
catenated. The two rings are related by a center of symmetry,
and the intermolecular distance Au ؒ ؒ ؒ Au = 3.074(1) Å
(Fig. 1a), with associated torsion angles C–Au ؒ ؒ ؒ Au–C =
50.2Њ and P–Au ؒ ؒ ؒ Au–P = 49.7Њ, similar to the values in 3g
and well-suited for formation of a strong aurophilic attraction.
The transannular Au ؒ ؒ ؒ Au distance is 7.890 Å, considerably
longer than in 3g as a result of the longer spacer group of
the diphosphine, and this gives rise to a larger, more circular,
cavity in 3d compared to 3g. The conformation of the flex-
ible diacetylide ligand is different in the two complexes (Figs. 1a
and 2a) to accommodate the different transannular gold–gold
Fig. 2 The molecular structure of complex 3d, [1,2-C2H4(O-3-C6-
᎐
H4OCH2C᎐CAu)2(µ-Ph2P(CH2)4PPh2)]2, with hydrogen atoms omitted
᎐
for clarity: (a) the ring structure and intermolecular aurophilic
bonding, and (b) a space-filling model showing the phenyl group of one
molecule penetrating the cavity of the other. Symmetry operations for
equivalent atoms: Ϫx ϩ 1, Ϫy, Ϫz ϩ 1.
and it is clear that the combination of strong aurophilic attrac-
tions, combined with several weaker aryl–aryl attractions,
favors the side-by-side association found for 3d.
Luminescence spectra
Luminescence spectra were recorded at room temperature for
the gold() complexes 3, in both the solid state and in dichloro-
methane solution, and the results are summarized in Table 3.
Based on assignments for other alkynyl(phosphine)gold()
complexes, the emission is likely to occur from a triplet excited
state formed primarily by σ(AuC)/Au(5d)–π*/Au(6p) exci-
tation, and a significant red shift is expected when secondary
Au ؒ ؒ ؒ Au bonding is present and perturbs the energy levels.12
A single broad emission band was observed in each case for
complexes 3, with no resolved fine structure. The emission
maxima for 3a and 3b are similar in the solution and solid state
spectra (no more than 6 nm difference, Table 3), suggesting
similar structures in the two phases. For the diphosphine lig-
ands Ph2P(CH2)nPPh2, with n = 1 (3a) or 2 (3b), the bite distance
is small enough to allow transannular Au ؒ ؒ ؒ Au bonding and
this leads to formation of a narrow cavity in the macrocycle. It
is likely that the close association of pairs of rings in the solid
state, proved crystallographically for 3d and 3g, is not present in
the solid state structures of 3a and 3b. For the other complexes,
distances. Other comparative transannular dimensions for 3d
᎐
are 11.51 Å between the opposite OCH C᎐C atoms (11.12 Å in
᎐
2
3g), and 8.09 Å between the OCH2CH2 and Ph2PC atoms (9.41
Å in 3g). The diphosphine ligands in both 3d and 3g both tend
to adopt the anti conformation,12,13 but this is not compatible
with ring formation. Still, neither adopts the syn conform-
ation, but intermediate forms are preferred with dihedral
angles Au(1)–P(1)–P(2a)–Au(2a) = 58Њ and 71Њ in 3d and 3g,
respectively.
The similarity of the structures of 3d and 3g extends to the
nature of the self-recognition, with a phenylphosphorus group
of one ring completely enclosed in the cavity of the other, as
shown in Fig. 2b. The larger cavity of 3d allows deeper pene-
tration than in 3g (compare Figs. 2b and 1b). The ligand bis-
(diphenylphosphino)butane has previously been shown to be
ideal for formation of [2]catenanes of type E (Chart 1,
25-membered ring when n = 4),7d and we had anticipated that 3d
might form a similar structure. However, this was not the case
J. Chem. Soc., Dalton Trans., 2002, 2885–2889
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᎐
Table 3 Luminescence data for the complexes
[1,2-C H (O-3-C H OCH C᎐CAu) ] , 2. A solution of 1
᎐
2
4
6
4
2
2 n
(0.109 g, 0.340 mmol) and sodium acetate (0.140 g, 1.698
mmol) in THF (10 mL)–MeOH (10 mL) was added to a sus-
pension of [AuCl(SMe2)] (0.200 g, 0.679 mmol) in 1 : 1 THF–
MeOH (20 mL), and the resultant mixture was stirred for 1 h at
0 ЊC. The mixture was filtered, and the yellow solid was washed
with THF, MeOH and pentane (Yield 56%). The solid was
insoluble in common organic solvents, and was light sensitive,
so could not be purified and was characterized by its reactions
Complex
Medium
Emission max/nm
3a
3b
3c
3d
3e
3f
Solid
CH2Cl2
Solid
CH2Cl2
Solid
CH2Cl2
Solid
CH2Cl2
Solid
CH2Cl2
Solid
CH2Cl2
Solid
CH2Cl2
Solid
470
464
450
455
468
410
486
433
467
426
469
412
467
430
468
418
described below. IR (Nujol): ν(C᎐C) 2000 cmϪ1. Anal. Calc. for
᎐
᎐
C20H16O4Au2ؒ2NaCl: C, 28.9; H, 1.9. Found: C, 29.0; H, 1.9%.
᎐
[1,2-C H (O-3-C H OCH C᎐CAu) (ꢀ-dppm)], 3a. A solution
᎐
2
4
6
4
2
2
of dppm (0.062 g, 0.16 mmol) in CH2Cl2 (10 mL) was added to
a suspension of 2 (0.116 g, 0.14 mmol) in CH2Cl2 (10 mL). The
mixture was stirred for 3 h, treated with decolorizing charcoal
(100 mg), stirred for 15 min, filtered, and the product was pre-
cipitated from the solution by addition of pentane. A colorless
solid was collected by filtration, washed with ether, and dried
(Yield 61%). NMR (CD2Cl2): δ(1H) 7.3–7.6 [m, 22H; Ph and
o-HAr], 7.29 [br, 2H, H–C5Ar], 6.82 [s, 2H, H–C2Ar], 6.55
[br, 2H, H–C4 or 6Ar], 4.69 [s, 4H; CH2CC], 4.33 [s, 4H; OCH2-
3g
3h
CH2Cl2
λ(excitation) was 350 nm in each case.
3c–3h, the diphosphines do not allow close enough approach of
the gold atoms for formation of transannular Au ؒ ؒ ؒ Au bond-
ing, and so the emission in solution occurs at higher energy
(410–430 nm range) compared to 3a (464 nm) or 3b (455 nm),
and similar to values obtained for other alkynyl(phosphine)-
gold() complexes which do not have Au ؒ ؒ ؒ Au bonding.4,5,7
In the solid state, there was a strong red shift in the emission
maximum for each of complexes 3c–3h, with band maxima in
the range 450–486 nm (shift of 41–58 nm), strongly suggesting
that intermolecular association occurs in each case. The data
for the structurally characterized complexes 3d (486 nm in
solid, 433 nm in CH2Cl2 solution) and 3g (467 nm in solid, 430
nm in CH2Cl2 solution) are typical, and so it is proposed that all
complexes 3c–3h self-associate in the solid state in the same
way.
31
᎐
CH O], 3.62 [s, 2H, dppm]; δ( P) 31.91 [s]. IR [Nujol): ν(C᎐C)
᎐
2
2132 cmϪ1. Anal. Calc. for C45H38O4P2Au2ؒ0.5CH2Cl2: C, 47.9;
H, 3.4. Found: C, 47.9; H, 3.2%. Similarly prepared were:
᎐
[1,2-C H (O-3-C H OCH C᎐CAu) (ꢀ-dppe)], 3b. Yield 35%.
᎐
2
4
6
4
2
2
NMR (CD2Cl2): δ(1H) 7.4–7.7 [m, 22H; Ph and o-HAr]; 7.21
3
[t, J(HH) = 8 Hz, 2H, H–C5Ar], 6.86 [s, 2H, H–C2Ar], 6.58
[d, 3J(HH) = 8 Hz, 2H, H–C4 or 6Ar], 4.79 [s, 4H, CH2CC], 4.32
[s, 4H, OCH2CH2O], 2.62 [s, 4H, dppe]; δ(31P) 40.04 [s]. IR
(Nujol): ν(C᎐C) 2130 cmϪ1. Anal. Calc. for C46H40O4P2Au2: C,
᎐
᎐
49.6; H, 3.6. Found: C, 50.0; H, 3.1%.
᎐
[1,2-C H (O-3-C H OCH C᎐CAu) (ꢀ-dppp)], 3c. Yield 43%.
᎐
2
4
6
4
2
2
NMR(CD2Cl2): δ(1H) 7.2–7.7 [m, 22H; Ph and o-HAr], 7.17
[t, 3J(HH) = 8 Hz, 2H, H–C5Ar], 6.60 [m, 6H, Ar], 4.79 [s, 4H,
CH2CC], 4.29 [s, 4H, OCH2CH2O], 2.79 [m, 4H, dppp], 1.87
Experimental
31
Ϫ1
᎐
[m, 2H, dppp]; δ( P) 33.73 [s]. IR (Nujol): ν(C᎐C) 2132 cm
.
᎐
NMR spectra were recorded by using a Varian Gemini 300
MHz spectrometer, with 1H NMR chemical shifts reported
relative to TMS and 31P chemical shifts reported relative to an
85% H3PO4 external standard. IR spectra were recorded as
Nujol mulls using a Perkin-Elmer 2000 FTIR. Emission spectra
were recorded at room temperature using a Fluorolog-3
spectrofluorimeter. For recording the emission and excitation
spectra, solutions were placed in quartz cuvettes, while solid
samples were ground finely, in some cases with added KBr. A 1
nm slit width was used for the solid samples and a 3 nm slit
width for the solutions. CAUTION! Gold acetylides are poten-
tially shock sensitive and should be handled in small quantities
using protective equipment.
Anal. Calc. for C47H42O4P2Au2ؒCH2Cl2: C, 47.6; H, 3.7. Found:
C, 48.0; H, 3.8%.
᎐
[1,2-C H (O-3-C H OCH C᎐CAu) (ꢀ-dppb)], 3d. Yield 33%.
᎐
2
4
6
4
2
2
NMR (DMSO): δ(1H) 7.4–7.7 [m, 22H; Ph and o-HAr], 7.16
3
[t, J(HH) = 8 Hz, 2H, H–C5Ar], 6.73 [s, 2H, H–C2Ar], 6.55
[d, 3J(HH) = 8 Hz, 2H, H–C4 or 6Ar], 4.72 [s, 4H, CH2CC], 4.25
[s, 4H, OCH2CH2O], 2.64 [m, 4H, dppb], 1.52 [m, 4H, dppb];
31
δ( P) 37.20 [s]. IR (Nujol): ν(C᎐C) 2131 cmϪ1. Anal. Calc. for
᎐
᎐
C48H44O4P2Au2: C, 50.5; H, 3.9. Found: C, 50.9; H, 4.0%.
᎐
[1,2-C H (O-3-C H OCH C᎐CAu) (ꢀ-dpppe)], 3e. Yield
᎐
2
4
6
4
2
2
31%. NMR (CD2Cl2): δ(1H) 7.4–7.6 [m, 22H; Ph and o-HAr],
7.17 [t, 3J(HH) = 8 Hz, 2H, H–C5Ar], 6.74 [s, 2H, H–C2Ar], 6.55
[d, 3J(HH) = 8 Hz, 2H, H–C4 or 6Ar], 4.75 [s, 4H, CH2CC], 4.33
[s, 4H, OCH2CH2O], 2.60 [m, 4H, dpppe], 2.41 [m, 4H, dpppe],
Synthesis
᎐
1,2-C H (O-3-C H OCH C᎐CH) , 1. A solution of 1,2-C H -
᎐
2
4
6
4
2
2
2
4
31
᎐
(O-3-C6H4OH)2 (2.50 g, 10.15 mmol), BrCH2CCH (2.42 g,
20.30 mmol) and K2CO3 (4.21 g, 30.45 mmol) in acetone
(100 mL) was heated under reflux for five days. The reaction
mixture was filtered to remove KBr, and the solvent was
removed under vacuum to give the product as a yellow oil. This
was extracted with ether, and the solution was washed with
aqueous NaHCO3, dried with MgSO4, filtered, and the solvent
removed under vacuum. Trituration ofthe product with pentane
afforded a yellow solid (Yield 70%). NMR in CDCl3: δ(1H)
1.64 [m, 2H, dpppe]; δ( P) 37.76 [s]. IR (Nujol): ν(C᎐C) 2132
᎐
cmϪ1. Anal. Calc. for C49H46O4P2Au2ؒCH2Cl2: C, 48.4; H, 3.9.
Found: C, 48.6; H, 4.0%.
᎐
[1,2-C H (O-3-C H OCH C᎐CAu) (ꢀ-dpph)], 3f. Yield 53%.
᎐
2
4
6
4
2
2
NMR (CD2Cl2): δ(1H) 7.3–7.7 [m, 22H; Ph and o-HAr], 7.20
3
[t, J(HH) = 8 Hz, 2H, H–C5Ar], 6.70 [s, 2H, H–C2Ar], 6.57
3
[d, J(HH) = 8 Hz, 2H, H–C4 6Ar], 4.75 [s br, 4H, CH2CC],
or
4.30 [s, 4H; OCH2CH2O], 2.46 [s br, 4H, dpph], 1.62 [s br, 4H,
4
31
᎐
6.20–7.23 [m, 8H; Ar], 4.67 [d, J(HH) = 2 Hz, 4H, CH2CC],
dpph], 1.45 [s, 4H, dpph]; δ( P) 32.53 [s]. IR (Nujol): ν(C᎐C)
᎐
4
4.30 [s, 4H, OCH2CH2O], 2.39 [t, J(HH) = 2 Hz, 2H, CCH);
2132 cmϪ1. Anal. Calc. for C50H48O4P2Au2ؒ0.5CH2Cl2: C, 50.1;
δ(13C) 102.10, 107.41, 107.69, 129.90, 158,.67, 159.69 [aryl];
78.44 [CCH]; 75.53 [CCH]; 55.77 [CH2CC]; 66.41 [OCH2-
H, 4.1. Found: C, 49.5; H, 4.3%.
᎐
᎐
᎐
CH O]. IR (Nujol): ν(C᎐C) 2116, ν(C᎐CH) 3289 and 3267
[1,2-C H (O-3-C H OCH C᎐CAu) (ꢀ-dppee)], 3g. Yield
᎐
᎐
᎐
2
2
4
6
4
2
2
cmϪ1; EI–MS: m/z: 322.120, calc. for C20H18O4: 322.120.
62%. NMR (CD2Cl2): δ(1H) 7.45–7.60 [m, 22H; Ph and o-HAr],
2888 J. Chem. Soc., Dalton Trans., 2002, 2885–2889

View Article Online
Table 4 Crystal data and structure refinement
See http://www.rsc.org/suppdata/dt/b2/b201832b/ for crystal-
lographic data in CIF or other electronic format.
3d
3g
Formula
FW
C49.5H49Au2ClO4.5P2
1207.21
C46H38Au2O4P2
1110.64
Acknowledgements
We thank the NSERC (Canada) for financial support and for a
scholarship to W. J. H., and Dr M. C. Jennings for the X-ray
data collection for complex 3g. R. J. P. thanks the Government
of Canada for a Canada Research Chair.
T /K
λ/Å
Crystal system
Space group
a/Å
223(2)
0.71073
Monoclinic
P21/c
10.6544(6)
27.827(1)
16.5665(9)
98.377(1)
4859.3(5), 4
1.65
200(2)
0.71073
Monoclinic
P21/n
14.7711(5)
15.2895(5)
18.3486(8)
107.100(2)
3960.7(3), 4
1.86
b/Å
c/Å
β/Њ
References
Volume/Å3, Z
D(calc)/Mg mϪ3
Absorption coefficient/
mmϪ1
1 (a) S. Leininger and P. J. Stang, Chem. Rev., 2000, 100, 853;
(b) P. J. Stang and B. Olenyuk, Acc. Chem. Res., 1997, 30, 502;
(c) M. Fujita and K. Ogura, Coord. Chem. Rev., 1996, 148, 249.
2 Comprehensive Supramolecular Chemistry, J. L. Atwood, J. E. D.
Davies, D. D. MacNicol, F. Vögtle and K. S. Suslick, eds., Pergamon
Press, Oxford, 1996.
6.194
7.524
F(000)
2348
25358/8550
2136
35062/9050
Reflections/
independent reflections
Absorption correction
R1/wR2 [I > 2σ(I )]
3 M. H. Keefe, K. D. Benkstein and J. T. Hupp, Coord. Chem. Rev.,
2000, 205, 201.
Integration
0.1061/0.2817
SADABS
0.0416/0.0993
4 (a) V. W. W. Yam, K. K. W. Lo and M. C. Wong, J. Organomet.
Chem., 1999, 578, 3; (b) M. J. Irwin, J. J. Vittal and R. J. Puddephatt,
Organometallics, 1997, 16, 3541; (c) C. M. Che, H. K. Yip, W. C. Lo
and S. M. Peng, Polyhedron, 1994, 13, 887; (d ) C. M. Che,
H. Y. Chao, V. M. Miskowski, Y. Li and K. K. Cheung, J. Am.
Chem. Soc., 2001, 123, 4985.
5 (a) V. W. W. Yam, C. K. Li and C. L. Chan, Angew. Chem., Int. Ed.,
1998, 37, 2856; (b) B. C. Tzeng, W. C. Lo, C. M. Che and S. M. Peng,
Chem. Commun., 1996, 181; (c) B. C. Tzeng, K. K. Cheung and
C. M. Che, Chem. Commun., 1996, 1681; (d ) A. Burini, R. Bravi,
J. P. Fackler Jr., R. Galassi, T. A. Grant, M. A. Omary, B. R.
Pietroni and R. J. Staples, Inorg. Chem., 2000, 39, 3158; (e) W. H.
Chan, T. C. W. Mak and C. M. Che, J. Chem. Soc., Dalton Trans.,
1998, 2275; ( f ) J. C. Vickery, M. M. Olmstead, E. Y. Fung and
A. L. Balch, Angew. Chem., Int. Ed. Engl., 1997, 36, 1179; (g) E. Y.
Fung, M. M. Olmstead, J. C. Vickery and A. L. Balch, Coord. Chem.
Rev., 1998, 171, 151; (h) R. H. Uang, C. K. Chan, S. M. Peng and
C. M. Che, J. Chem. Soc., Chem. Commun., 1994, 2561.
7.15 [t, 3J(HH) = 8.0 Hz, 2H, H–C5Ar], 6.98 [t, J(HP) = 18.1 Hz,
2H, dppee], 6.74 [s, 2H, H–C2Ar], 6.53 [d, 3J(HH) = 7.5 Hz, 2H,
H–C4 6Ar], 4.78 [s, 4H; CH2CC], 4.31 [s, 4H; OCH2CH2O];
or
31
δ( P) = 39.05 [s]. IR (Nujol): ν(C᎐C) 2132 cmϪ1. Anal. Calc. for
᎐
᎐
C46H38O4P2Au2: C, 49.7; H, 3.4. Found: C, 49.5; H, 3.3%.
᎐
[1,2-C H (O-3-C H OCH C᎐CAu) (ꢀ-dppa)], 3h. Yield 35%.
᎐
2
4
6
4
2
2
NMR (CD2Cl2): δ(1H) 7.4–7.7 [m, 22H; Ph and o-HAr], 7.18
3
[t, J(HH) = 8 Hz, 2H, H–C5Ar], 6.79 [s, 2H, H–C2Ar], 6.55
[d, 3J(HH) = 8 Hz, 2H, H–C4 or 6Ar], 4.81 [s, 4H, CH2CC], 4.33
31
᎐
[s, 4H, OCH CH O]; δ( P) 17.50 [s]. IR (Nujol): ν(C᎐C–Au)
᎐
2
2
2129, ν(C᎐CP) 2065 cmϪ1. Anal. Calc. for C46H36O4P2Au2: C,
᎐
᎐
49.8; H, 3.3. Found: C, 49.6; H, 3.1%.
6 (a) A. Grohmann and H. Schmidbaur, in Comprehensive
Organometallics II, E. W. Abel, F. G. A. Stone and G. Wilkinson,
eds., Elsevier, Oxford, 1995, vol. 3, pp. 1–56; (b) R. J. Puddephatt, in
Comprehensive Coordination Chemistry, G. Wilkinson, R. D. Gillard
and J. A. McCleverty, eds., Pergamon Press, Oxford, 1987, vol. 5,
pp. 861–923; (c) H. Schmidbaur, ed., Gold: Progress in Chemistry,
Biochemistry and Technology, Wiley: Chichester, 1999.
7 (a) W. J. Hunks, M. A. MacDonald, M. C. Jennings and R. J.
Puddephatt, Organometallics, 2000, 19, 5063; (b) M. J. Irwin,
L. M. Rendina, J. J. Vittal and R. J. Puddephatt, Chem. Commun.,
1996, 1281; (c) M. A. MacDonald and G. P. A. Yap, Organo-
metallics, 2000, 19, 2194; (d ) C. P. McArdle, M. J. Irwin, M. C.
Jennings and R. J. Puddephatt, Angew. Chem., Int. Ed., 1999, 38,
3376; (e) C. P. McArdle, J. J. Vittal and R. J. Puddephatt, Angew.
Chem., Int. Ed., 2000, 39, 3819; ( f ) R. J. Puddephatt, Chem.
Commun., 1998, 1055; (g) C. P. McArdle, M. C. Jennings, J. J. Vittal
and R. J. Puddephatt, Chem. Eur. J., 2001, 7, 3573; (h) R. J.
Puddephatt, Coord. Chem. Rev., 2001, 216–217, 313.
X-Ray data collection and structure determination
Crystals of 3g were grown by slow diffusion of ether into a
solution in dichloromethane at 4 ЊC. A tiny, colourless plate
was mounted on a glass fibre. Data were collected at 200 K
using a Nonius Kappa-CCD diffractometer using COLLECT
(Nonius, 1998) software. The unit cell parameters were
calculated and refined from the full data set. Crystal cell refine-
ment and data reduction was carried out using the Nonius
DENZO package. The data were scaled using SCALEPACK
(Nonius, 1998) and no other absorption corrections were
applied. The crystal data and refinement parameters are listed
in Table 4.
The SHELXTL 5.1 program package was used to solve the
structure by Patterson methods and refinement was by full-
matrix least squares on F 2.14 All non-hydrogen atoms were
refined with anisotropic thermal parameters. The hydrogen
atoms were calculated geometrically and were riding on their
respective carbon atoms. The largest residual electron density
peak (2.383 e ÅϪ3) was associated with one of the gold atoms.
The data for 3dؒ0.5CH2Cl2ؒ0.5H2O were collected at Ϫ50 ЊC
using a Siemens SMART 1K CCD diffractometer. The
structure was solved using direct methods, completed by sub-
sequent Fourier syntheses, and refined by full-matrix least-
squares on F 2 using SHELXTL 5.10.14 All atoms were refined
anisotropically, except hydrogen atoms, which were treated as
idealized contributions. Empirical absorption corrections were
applied using SADABS.15 No special constraints or restraints
were applied in solving structure 3d. The molecule was posi-
tioned on the inversion center in the monoclinic space group
P21/c, and showed possible disorder, although this could not be
refined successfully. There are large residuals, and the structure
determination was only partly successful, but the connectivity is
established.
8 (a) J. G. Hansen, N. Feeder, D. G. Hamilton, M. J. Gunter, J. Becher
and J. K. M. Sanders, Org. Lett., 2000, 2, 449; (b) G. R. Desiraju,
Acc. Chem. Res., 1996, 29, 441; (c) M. J. Calhorda, Chem. Commun.,
2000, 801.
9 R. J. Cross and M. F. Davidson, J. Chem. Soc., Dalton Trans., 1986,
411.
10 D. M. P. Mingos, J. Yau, S. Menzer and D. J. Williams,
Angew. Chem., Int. Ed. Engl., 1995, 34, 1894.
11 (a) P. Pyykkö, Chem. Rev., 1997, 97, 597; (b) S. S. Pathaneni and
G. R. Desiraju, J. Chem. Soc., Dalton Trans., 1993, 319; (c) P.
Pyykkö, J. Li and N. Runeberg, Chem. Phys. Lett., 1994, 218, 133;
(d ) J. Li and P. Pyykkö, Chem. Phys. Lett., 1992, 197, 586.
12 (a) M. J. Irwin, J. J. Vittal and R. J. Puddephatt, Organometallics,
1997, 16, 3541; (b) W. E. van Zyl, J. M. Lopez-de-Luzuriaga and
J. P. Fackler Jr., J. Mol. Struct., 2000, 516, 99.
13 M. C. Brandys, M. C. Jennings and R. J. Puddephatt, J. Chem. Soc.,
Dalton Trans., 2000, 4601.
14 G. M. Sheldrick, SHELXTL 5.10 for Windows: Structure
Determination Software Programs, Bruker Analytical X-Ray
Systems, Inc., Madison, WI, 1997.
15 G. M. Sheldrick, SADABS: Program for Empirical Absorption
Correction of Area Detector Data, University of Göttingen,
Germany, 1998.
CCDC reference numbers 181890 (3g) and 181891 (3d).
J. Chem. Soc., Dalton Trans., 2002, 2885–2889
2889